Coeroxane compounds



Patented July 22, 1941 COEROXANE COMPOUNDS Eugene A. Markush, Jersey City, N. J., John J. Malawista, Brooklyn, N. Y., and Julius Miller, Newark, N. J., assignors to Pharma Chemical Corporation, New York, N. Y., a corporation of New York N Drawing. Application March 31, 1938, Serial No. 199,188

1 Claim.

Our invention relates to the production of new coeroxane compounds and refers particularly to the esters and ethers of coeroxane.

Coeroxene and its heretofore known derivatives (Cl. zoo-ass) R may be alkyl, aralkyl, aryl (or substitution products thereof), or the residue of an acid group of the fatty series, or aromatic series, or heterocyclic type.

are described inLiebigs Annalen der Chemie,vol- The following examples illustrate in part the ume 348, pages 210-239, volume 356, pages preparation of some of the newly invented com- 317-325, and in English Patents 447,469 and pounds: 448,180. EXAMPLE 1 We have discovered, contrary to expectation,. that ethers and esters of 4:14 dimethyl coerox- Alkylatwn 01101-9 (as for example Annalen 356, 324, the A mixture of 50 grams 4114 dlmethyl-coeroxmethyl or ethyl ether) are readily reducible to owl-9, 450 Water, 100 grams sodium-hydroxthe corresponding coeroxane compounds which e 0% solution) are heated to 80 u 37 are yellow bodies of excellent solubility in ora methyl-sulfate are added p The ganic solvents, oils, and waxes, and which impart temperature 11868 130 ab ThlS t pe to these solvents strong, brilliant fluorescence. 'e is maintained for one hour; the mixture is Both the aforementioned patents and literature Cooled, d l With W the preclplvtate deal only with the reduction of the dimethyl cod} a drled- Yield, 44 grams of eroxon t thektdimethyl coeroxene and djmethyl ethyl ether of 4:14d1methyl-coeroxonol 9. M. P. coeroxenol acetate. 1444507 i The general procedure of the reaction in our 7 Reduction invention is A mixture of 44' grams 4:14 dimethyl-ethoxy- 6 coeroXonol-9, 250 grams water, 50 grams zinc A I 7 5 dust; 125 grams water, and 100 grams sodium hy- 7 5 droxideare heated for 5 hours at 90100 C. The 8 l 8 reaction, mixture is cooled, diluted, filtered, the i precipitate washed with hot-water containing a 10052 little caustic soda until the washings are color- 15 9 15 09 less and then washed with water until free of caustic soda. F I 1 011314 I 40113 The precipitate containing zinc is added in 16 13 i 3 small portions to concentrated hydrochloric acid 0 1 0 and stirred until all the inc is dissolved, diluted 2 12 16 2 with water, the precipitate filtered, Washed, and the latter being the probable general formula of dried. Yield, 37.5 grams. our newly discovered compounds and in which The probable reaction is:

I. II.

8 CgHsO 10 =0 pr on :0

(C2H5)2SO4 cm CHi 0113 161/ 13 i 16 i2 :2 12 2 NaOH i Z 4,14 dimethyl coeroxono1-9 4,14 dimethyl coeroxonol-Q- ethyl ether 4,14 dimethyl-Q-cthoxy coeroxane The compound is soluble in oils with a greenish yellowfluorescence.

EXAMPLE II Alkylation A mixture of 50 grams 4:14 dimethyl-coeroxonol-9, 450 cc. water, 100 grams sodium hydroxide 50% solution are heated to 90 C'., cooled to 50 0., and 30 grams dimethyl-sulfate are added at once. The temperature rises to 56 C. The mixture is held at this temperature for one hour, cooled, diluted with water, the precipitate filtered, washed, and dried. Yield, 40 grams of 4:14 dimethylcoeroxonol Q-methylether. M. P. 105.

Reduction and stirred until all'the zinc is dissolved, diluted with water, the precipitate filtered, washed, and

dried. Yield, 30.5 grams. 7

This methyl compound is somewhat better soluble in oils with greenish yellow fluorescence. The probable formula is:

50 parts of 4:14 dimethyl-coeroxonol-9 are stirred into 450 parts of glacialacetic acid and 100 parts of acetic anhydride. The reaction mass 7 is heated to the boiling point and refluxed for 3 hours and allowed to stand until the next day.

25'parts of zinc dust are carefully added and the mixture again refluxed for 3 hours. At the end of ;,thep'eriod the color of the reaction mass assumes a pronounced yellow tone from the original'violet brown of the initial reaction.

The massis allowed to cool and discharged into a large volume of water. After filtering, washing I mula is:

the press cake until free ofacid, and drying there is obtained 40 parts of an olive-yellow powder which is clearly soluble in alcohols and ethers. It imparts a bright yellow fluorescence to the solvent used.

Its probable formula is:

CHaCO I l l H' EXAMPLEIV 50 parts of propylether of 4:14 dimethyl coeroxonol-Q prepared by refluxing the 4:14 dimethyl-coeroxono1-9 with excess propyl alcohol are reduced and isolated according to the procedure described in Example I.

The yellow orange powder, yield 50 parts, dissolves in organic solvents with a bright yellow coloration and imparts a powerful yellow fluorescence and pearliness to the solvent employed.

The probable formula is:

EXAMPLE V By substituting the corresponding iso-butylether prepared by boiling 4:14 dimethyl-coeroxonol-9 with iso-butyl alcohol, there is obtained in good yield the compound whose probable for- (CHahCH-CHzO This orange colored body dissolves in organic solvents and imparts a powerful fluorescence somewhat bluer than either the propyl or the ethyl compounds.

EXAMPLE VI To a solution of 50 parts sodium hydroxide in 500 parts water are added 50 parts 4: 14 dimethylcoeroxonol-9 and the reaction mixture heated to C. At this temperature, with good stirring, 40 /2 parts of benzoyl chloride are added slowly.

The temperature rises to 90 C., where it is maintained for 2 hours. Minimum alkalinity of pH 8 should be maintained.

The mixture is allowed to cool, diluted with two volumes of water, and filtered. The cake is washed with a sodium hydroxide solution and then with cold water until free of alkali and then dried. The yield is 50 parts of the benzoyl ester. The ester is then reduced by prolonged boiling in glacial acetic acid parts for 1 part ester) and zinc dust /2 part for 1 part ester). After cooling and diluting with water the reduced body is removed by filtering, then washed well, and dried. Oil-insoluble bodies, such as zinc, are removed by dissolving the product in benzol or toluol or other low boiling organic solvents, filtering from insolubles, and distilling the solvent.

From 50 parts of benzoyl ester of 4:14 dimethyl-coeroxonol-9 there are obtained 43 to 4.7 parts of a bright orange powder which, when dissolved in mineral oil, imparts a bright yellow fluorescence. The probable formula of the body is:

| 1 A H I u H H I I H\ co--o\ 10o H H 9 CH3 CH3 50 parts of 4:14 dimethyl-coeroxonol-Q are added to a solution of 50 parts sodium hydroxide in 500 parts of water. 40 parts of benzyl chloride are added and the reaction mass stirred at 30-35 0., for several days. After filtering, washing with diluted sodium hydroxide solution (5%), and then with water, the benzyl ether of 4:14 dimethyl coeroxonol-Q is obtained. When reduced according to the method described in Example 1, a brownish powder is obtained which imparts a greenish-yellow fluorescence to organic solvents.

Its probable formula is:

We do not limit ourselves to the particular chemicals, quantities, times, temperatures, or other steps of procedure specifically mentioned as these are given simply for the purpose of clearly describing our invention.

What we claim is:

Compounds having the general formula in which R is the radical of a member of the group consisting of aliphatic hydrocarbon, aralkyl hydrocarbon and heterocyclic compounds.

EUGENE A. MlARKUSH. JOHN J. MALAWISTA. JULIUS MILLER. 

